CN105457679B - A kind of ethylene oligomerization carbon monoxide-olefin polymeric and its application - Google Patents
A kind of ethylene oligomerization carbon monoxide-olefin polymeric and its application Download PDFInfo
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Abstract
The invention discloses a kind of ethylene oligomerization carbon monoxide-olefin polymeric, including shown in formula (I) major catalyst pyridinium chloride base contracting imines close iron (II) complex, containing aluminum cocatalyst and organic solvent：In formula, R1~R10It is identical or different, it is each independently selected from hydrogen, C1~C6Alkyl, halogen, C1~C6Alkoxy and nitro；R11And R12It is identical or different, independently selected from hydrogen, C1‑C6Alkyl, C6‑C10Aryl, C7‑C15Alkaryl and C7‑C15Aralkyl.Ethylene oligomerization reaction process is used for using carbon monoxide-olefin polymeric of the present invention, there is very high oligomerisation reaction activity, the selectivity of alhpa olefin is high, and oligomerisation reaction initiation is rapid, operates steadily, be reproducible；Even in low aluminium/iron ratio, still with extraordinary oligomerisation reaction activity；This just overcomes the technology prejudice of those skilled in the art, achieves unexpected technique effect, and catalytic effect and cost are preferably balanced so that ethylene oligomerization reaction cost declines to a great extent, practical, and industrial prospect is wide.
Description
Technical field
The present invention relates to ethylene oligomerization field, and in particular to a kind of catalyst combination for ethylene oligomerization reaction process
Thing.
Background technology
Linear alpha-alkene ethylene comonomer, synthesis of surfactant intermediate, plasticizer alcohol, synthetic lubricant fluid and
The fields such as oil dope have a wide range of applications.In recent years, with the continuous development of polyolefin industry, in world wide to α-
The demand rapid development of alkene.The alpha-olefin of the overwhelming majority is prepared to obtain by ethylene oligomerization at present.
Catalyst used in ethylene oligomerization method mainly has nickel system, chromium system, zirconium system and aluminium system etc., and in recent years, Brookhart is small
Group (Brookhart, M et al., J.Am.Chem.Soc., 1998,120,7143-7144；WO99/02472,1999), Gibson
Group (Gibson, V.C. et al., Chem.Commun., 1998,849-850；Chem.Eur.J., 2000,2221-2231) point
Ethylene oligomerization can be catalyzed by not finding some Fe (II) and Co (II) trident pyridinimine complex, and in co-catalyst methyl
Under aikyiaiurnirsoxan beta effect, not only the catalytic activity of catalyst is very high, and the selectivity of alpha-olefin is also very high.Therefore this kind of complex
There is very strong prospects for commercial application.But either MAO, or modified methylaluminoxane all exist as co-catalyst
The problem of cost is too high, and dosage is excessive, as co-catalyst large-scale application when the ethylene oligomerization, it certainly will cause production cost
It is high.
Today, it is generally accepted that water is very unfavorable to ethylene oligomerization reaction process, as CN200810111717.8 is disclosed
A kind of method of ethylene oligomerization, it is strict controlled in the environment of anhydrous and oxygen-free and carries out, therefore the reaction pair of current ethylene oligomerization
Technological requirement is very harsh, causes the reaction initiation of oligomerisation reaction technique and repeatability all excessively poor.
The content of the invention
For deficiency of the prior art, inventor has carried out grinding extensively and profoundly in ethylene oligomerization with catalyst field
Study carefully, it has surprisingly been found that ethene is matched somebody with somebody including the major catalyst chlorination DAP contracting amine conjunction iron (II) shown in formula (I)
Compound, the lower progress oligomerisation reaction of carbon monoxide-olefin polymeric effect containing aluminum cocatalyst, water and organic solvent, have higher on the contrary
Oligomerisation reaction activity, and oligomerisation reaction initiation is rapid, operates steadily, be reproducible；So as to overcome those skilled in the art's
Technology prejudice, achieve unexpected technique effect.
According to an aspect of the invention, there is provided a kind of ethylene oligomerization carbon monoxide-olefin polymeric, the composition include
Major catalyst pyridinium chloride base contracting imines shown in formula (I) closes iron (II) complex, containing aluminum cocatalyst and organic solvent：
In formula, R1~R10It is identical or different, it is each independently selected from hydrogen, C1~C6Alkyl, halogen, C1~C6Alkoxy and
Nitro；R11And R12It is identical or different, independently selected from hydrogen, C1-C6Alkyl, C6-C10Aryl, C7-C15Alkaryl and C7-
C15Aralkyl.
According to carbon monoxide-olefin polymeric provided by the invention, there is higher ethylene oligomerization reactivity, the selection of alpha-olefin
Property it is high.
In carbon monoxide-olefin polymeric of the present invention, using the weight of organic solvent as calculating benchmark, the weight content of water
(i.e. the organic solvent based on 1g, 5~350 × 10 are contained in composition for 5~350ppm-6G water), preferably 20~260ppm, most
Preferably 50~200ppm.In the range of described water content, the carbon monoxide-olefin polymeric has higher ethylene oligomerization activity.
In the carbon monoxide-olefin polymeric of the present invention, the dosage of the major catalyst and co-catalyst can according to production scale and
The process conditions during concrete applications such as production equipment are selected.In a specific embodiment of the carbon monoxide-olefin polymeric,
Using the volume of organic solvent as calculating benchmark, the content of the major catalyst is (organic molten i.e. based on 1L for 2~500 μm of ol/L
Agent, 2~500 × 10 are contained in composition-6Mol major catalyst), preferably 20~100 μm of ol/L.
In the present invention, wherein the mol ratio of aluminium in the co-catalyst and the iron in the major catalyst for 30 to small
In 900, preferably 100~700.In a specific embodiment of the above method, the mol ratio of the aluminium and iron is 148~196.
In the relatively low molar ratio range of offer, the ethylene oligomerization activity in methods described is still higher.
According to a preferred embodiment of the present invention, in the major catalyst, the R11And R12It is identical or not
Together, independently selected from selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, butyl, phenyl, phenyl methyl, phenylethyl and substitution
Phenyl.According to a further advantageous embodiment of the invention, R1~R10It is identical or different, independently selected from hydrogen, methyl, second
Base, n-propyl, isopropyl, fluorine, chlorine, bromine, methoxyl group, ethyoxyl and nitro.
In a specific embodiment, the R in the major catalyst11And R12For methyl, the also knot as shown in Formula II
Structure：
In formula, R1-R10Restriction be same as above.
In another specific embodiment according to the present invention, the R in the major catalyst1、R6、R11And R12For methyl,
R2-R5And R7-R10It is hydrogen.
In the present invention, the organic solvent be selected from toluene, hexamethylene, ether, tetrahydrofuran, ethanol, benzene, dimethylbenzene and
Dichloromethane, it is preferably selected from toluene and dimethylbenzene.
In the present invention, term " C1-C6Alkyl " refers to saturated straight chain or branched hydrocarbyl containing 1-6 carbon atom.Make
For C1-C6Alkyl, it can be mentioned that methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, positive penta
Base, isopentyl, sec-amyl, n-hexyl and Sec-Hexyl；Particularly preferred methyl, ethyl, n-propyl and isopropyl.
In the present invention, term " C1-C6Alkoxy " refers to above-mentioned C1-C6Alkyl is connected what is obtained with an oxygen atom
Group.As C1-C6Alkoxy, it can be mentioned that methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, isobutyl oxygen
Base, sec-butoxy, tert-butoxy, n-pentyloxy, secondary amoxy, positive hexyloxy and secondary hexyloxy；Particularly preferred methoxyl group and second
Epoxide.
In the present invention, term " halogen " refers to fluorine, chlorine, bromine and iodine, particularly preferred fluorine, chlorine and bromine.
In the present invention, term " C6-C10Aryl " refer to the aromatic group containing 6-10 carbon atom, it can be mentioned that benzene
Base, naphthyl etc..
In the present invention, term " C7-C15Alkaryl " refer to losing on the aromatic ring of the alkane aromatic hydrocarbons containing 7-15 carbon atom
The group for going hydrogen atom to be formed, such as tolyl, ethylbenzene, 3,5-dimethylphenyl, trimethylphenyl.
In the present invention, term " C7-C15Aralkyl " refer to that the alkyl of the aralkyl hydrocarbon containing 7-15 carbon atom loses
The group that hydrogen atom is formed, such as phenyl methyl, phenylethyl.
In the present invention, it is described to be selected from aikyiaiurnirsoxan beta and alkyl aluminum compound, preferably alkyl aluminum compound containing aluminum cocatalyst.
In the present invention, the formula of the alkyl aluminum compound is AlRnXm, wherein R is each independently straight or branched
C1-C8Alkyl；X is respectively halogen, preferably chlorine or bromine；N is 1~3 integer, and m is 0~2 integer, and m+n is equal to 3；It is preferred that
Ground, described alkyl aluminum compound are excellent from trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, three
Octyl aluminum, diethylaluminum chloride and ethylaluminium dichloride, more preferably triethyl aluminum.
In the present invention, the aikyiaiurnirsoxan beta is C1-C4Alkylaluminoxane, wherein C1-C4Alkyl is the alkane of straight or branched
Base；Preferably, described aikyiaiurnirsoxan beta is selected from MAO, modified methylaluminoxane, ethylaluminoxane and isobutyl aluminium alkoxide；
More preferably MAO.
Major catalyst chlorination 2,6- diacetyl pyridine contractings amine shown in the logical formula (II) of the present invention closes iron (II) complex can
It is made using the Chinese patent application CN101580488B preparation methods reported.
According to another aspect of the present invention, there is provided application of the above-mentioned carbon monoxide-olefin polymeric in ethylene oligomerization.Second
Alkene is carrying out oligomerisation reaction in the presence of the carbon monoxide-olefin polymeric, obtains ethylene oligomerization product.One of them is specific real
Applying example may include following steps：(1) dried by high temperature, the operation such as vacuum displacement enters line replacement to reaction system, it is ensured that reaction
Anhydrous and oxygen-free in system；(2) line replacement is entered to reaction system using ethene, reaction system is in ethene environment；(3) reacting
Carbon monoxide-olefin polymeric, including major catalyst, co-catalyst, water and organic solvent are added in system, is sufficiently stirred；(4) it is passed through second
Alkene starts oligomerisation reaction, keep reaction pressure be 0.1~30MPa and reaction temperature be reaction 30 at -20~150 DEG C~
100min；(5) stop reaction, take reaction product to carry out (GC) analysis with gas-chromatography.
In the present invention, the major catalyst described in step (3) and co-catalyst add after first being dissolved with organic solvent
Reaction system.The organic solvent is selected from toluene, hexamethylene, ether, tetrahydrofuran, ethanol, benzene, dimethylbenzene and dichloromethane,
It is preferably selected from toluene and dimethylbenzene.The oligomerisation reaction process, major catalyst and co-catalyst are blended under ethene atmosphere
OK.The temperature of the oligomerisation reaction is -20~150 DEG C, preferably 0~80 DEG C, more preferably 5~50 DEG C.The pressure of the reaction
Power is 0.1~30MPa, with ethylene pressure rise oligomerization activity rise.
Ethylene oligomerization is carried out using carbon monoxide-olefin polymeric of the present invention, the ethylene oligomerization product of acquisition includes C4、C6、
C8、C10、C12、C14、C16、C18、C20、C22Deng；The selectivity of alpha-olefin can reach more than 96%.Terminate in ethylene oligomerization reaction
Afterwards, GC analyses are carried out.As a result show, oligomerization activity is up to 107g·mol(Fe)-1·h-1More than.In addition, remaining reaction is mixed
The ethanol solution that compound is acidified with 5% watery hydrochloric acid neutralizes, and does not obtain polymer.
According to carbon monoxide-olefin polymeric provided by the invention, ethene is sub- including the major catalyst pyridinium chloride shown in formula (I)
Amine closes iron (II) complex, the lower progress oligomerisation reaction of composition effect containing aluminum cocatalyst, water and organic solvent, has on the contrary
Higher oligomerisation reaction activity, the selectivity of alpha-olefin is high, and oligomerisation reaction initiation is rapid, operates steadily, be reproducible.According to
The present invention, under the conditions of low-down Al/Fe ratios, still with preferable oligomerisation reaction activity.According to the present invention, when anti-
When should carry out at a lower temperature, still with high oligomerisation reaction activity.According to the present invention, those skilled in the art are overcome
Technology prejudice, achieve unexpected technique effect.
Embodiment
Below in conjunction with specific embodiment, the present invention is further elaborated and explanation, but does not form to any of the present invention
Limitation.
Embodiment 1
1. catalyst chlorination 2,6- diacetyl pyridines two (2-aminotoluene) close the synthesis of iron (II)
A.2,6- the synthesis of diacetyl pyridine two (2-aminotoluene)
4.94 grams of 2,6- diacetyl pyridines and 26 milliliters of ortho-aminotoluenes (grams per milliliter of density 0.9984) are added to 250 millis
Reactor is risen, adds 80 milliliters of absolute ethers, molecular sieve is added in reaction and makees water absorbing agent, keeps system micro- just under argon gas protection
0.150MPa is pressed, 1 milliliter of TiCl4 (grams per milliliter of density 1.726) was slowly added dropwise with 30 minutes, reacts 48 under solvent reflux temperature
After hour, rotary evaporation removes solvent, filtering, is washed three times with absolute ether, collects filtrate, be washed with water twice, separate organic
Layer, removal of solvent under reduced pressure, head product recrystallize in ethanol, obtain product DAP two (2-aminotoluene),
Yield 82.3%.1H NMR(CDCl3):δ8.38(d,2,HPyridine),7.86(t,1,HPyridine),7.20(m,4,HAryl),7.00(t,2,
HAryl),6.67(d,2,HAryl), 2.32 (s, 6, N=C-CH3), 2.10 (s, 6, aryl-CH3)。
B. chlorination 2,6- diacetyl pyridines two (2-aminotoluene) close the synthesis of iron (II)
Vacuumized in 100 milliliters of twoport reaction bulbs-applying argon gas repeatedly for three times after, argon gas protection under be separately added into
1.03 grams of 2,6- diacetyl pyridines two (2-aminotoluene) are used as part and 0.6 gram of FeCl2·4H2O, 30 milliliters of addition are anhydrous
Tetrahydrofuran, it is stirred at room temperature 2 hours, obtains black-and-blue solid, filters and washed three times with anhydrous tetrahydro furan, vacuum drying,
Preserved under argon gas.The final chlorination 2,6- diacetyl pyridines two (2-aminotoluene) that obtain close iron (II).Elementary analysis result：Reason
By value：C 59.00, H 4.95, N 8.97；Measured value：C 59.21, H 4.89, N 9.02.
2. ethylene oligomerization reacts, specifically comprise the following steps：(1) dried by high temperature, the operation such as vacuum displacement is to reaction
System enters line replacement, it is ensured that anhydrous and oxygen-free in reaction system；(2) line replacement is entered to reaction system using ethene, makes reaction system
In ethene environment；(3) water and toluene solvant are added in a kettle, and adding 1.37ml triethyl aluminums toluene solution, (concentration is
715 μm of ol/ml), add the toluene solution (concentration that 2ml chlorinations DAP two (2-aminotoluene) closes iron (II)
For 2.5 μm of ol/ml) after, it is 100ml to make total composition, wherein, using the weight of organic solvent (i.e. toluene) as calculating benchmark,
The weight content of water is 5ppm, Al/Fe=196, after being sufficiently stirred, is passed through ethene and starts oligomerisation reaction；(4) ethylene pressure is kept
It is to be reacted 30 minutes at 50 DEG C for 1MPa and reaction temperature；(7) stop reaction, take out a small amount of reaction product and carried out with gas-chromatography
(GC) analyze：Oligomerization activity is 0.56 × 107g·mol(Fe)-1·h-1, oligomer content is respectively C429.13%, C6~
C1057.12%, C6~C1869.65% (wherein containing linear alpha-alkene 94.5%), C20~C281.22%.Remaining mixture is used
The ethanol solution of 5% hydrochloric acid acidifying neutralizes, and does not obtain polymer.Analysis result is shown in Table 1.
Embodiment 2
With embodiment 1, difference is, the weight content of water is 20ppm.Data are shown in Table 1.
Embodiment 3
With embodiment 1, difference is, the weight content of water is 50ppm.Data are shown in Table 1.
Embodiment 4
With embodiment 1, difference is, the weight content of water is 120ppm.Data are shown in Table 1.
Embodiment 5
With embodiment 1, difference is, the weight content of water is 200ppm.Data are shown in Table 1.
Embodiment 6
With embodiment 1, difference is, the weight content of water is 260ppm.Data are shown in Table 1.
Embodiment 7
With embodiment 1, difference is, the weight content of water is 350ppm, and data are shown in Table 1.
Embodiment 8
With embodiment 1, difference is, the weight content of water is 120ppm, and reaction temperature is 40 DEG C.Data are shown in Table 1.
Embodiment 9
With embodiment 1, difference is, the weight content of water is 120ppm, and reaction temperature is 20 DEG C.Data are shown in Table 1.
Embodiment 10
With embodiment 1, difference is, the weight content of water is 120ppm, and reaction temperature is 10 DEG C.Data are shown in Table 1.
Embodiment 11
With embodiment 1, difference is, the weight content of water is 120ppm, and reaction temperature is 70 DEG C.Data are shown in Table 1.
Embodiment 12
With embodiment 1, difference is, the weight content of water is 120ppm, Al/Fe=500.Data are shown in Table 1.
Comparative example 1
With embodiment 1, difference is, anhydrous in composition.Data are shown in Table 1.
Table 1
"-" represents anhydrous in comparative example.
It can be seen from the data in Table 1 that according to carbon monoxide-olefin polymeric provided by the invention, ethene is including formula (I) Suo Shi
Major catalyst chlorination 2,6- diacetyl pyridines two (2-aminotoluene) close iron (II), containing aluminum cocatalyst, water and organic molten
The composition effect of agent is lower to carry out oligomerisation reaction, has higher oligomerisation reaction activity on the contrary, and the selectivity of alpha-olefin is high, and together
Poly- reaction initiation is rapid, operates steadily, be reproducible.According to the present invention, under the conditions of low-down Al/Fe ratios, still
With preferable oligomerisation reaction activity.It is when the reaction is performed at a lower temperature, still anti-with high oligomerisation according to the present invention
Should activity.
It should be noted that embodiment described above is only used for explaining the present invention, do not form to any of the present invention
Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that word wherein used is descriptive
With explanatory vocabulary, rather than limited vocabulary.The present invention can be made within the scope of the claims by regulation
Modification, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it relates to
And specific method, material and embodiment, it is not intended that the present invention is limited to wherein disclosed particular case, on the contrary, this hair
It is bright to can be extended to other all methods and applications with identical function.
Claims (24)
1. a kind of ethylene oligomerization carbon monoxide-olefin polymeric, including the major catalyst pyridinium chloride base contracting imines conjunction iron shown in formula (I)
(II) complex, containing aluminum cocatalyst, water and organic solvent：
In formula, R1~R10It is identical or different, it is each independently selected from hydrogen, C1~C6Alkyl, halogen, C1~C6Alkoxy and nitro；
R11And R12It is identical or different, independently selected from hydrogen, C1-C6Alkyl, C6-C10Aryl, C7-C15Alkaryl and C7-C15's
Aralkyl；
Using the weight of organic solvent as calculating benchmark, the weight content of water is 5~350ppm.
2. carbon monoxide-olefin polymeric according to claim 1, it is characterised in that in the major catalyst, the R11And R12
It is identical or different, independently selected from selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, butyl, phenyl, phenyl methyl, phenyl second
Base and substituted-phenyl；And/or R1~R10It is identical or different, independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, fluorine,
Chlorine, bromine, methoxyl group, ethyoxyl and nitro.
3. carbon monoxide-olefin polymeric according to claim 1, it is characterised in that in the carbon monoxide-olefin polymeric, with organic molten
The weight of agent is calculating benchmark, and the weight content of water is 20~260ppm.
4. carbon monoxide-olefin polymeric according to claim 1, it is characterised in that in the carbon monoxide-olefin polymeric, with organic molten
The weight of agent is calculating benchmark, and the weight content of water is 50~200ppm.
5. carbon monoxide-olefin polymeric according to claim 1, it is characterised in that in the carbon monoxide-olefin polymeric, with organic molten
The volume of agent is calculating benchmark, and the content of the major catalyst is 2~500 μm of ol/L.
6. carbon monoxide-olefin polymeric according to claim 5, it is characterised in that in the carbon monoxide-olefin polymeric, with organic molten
The volume of agent is calculating benchmark, and the content of the major catalyst is 20~100 μm of ol/L.
7. carbon monoxide-olefin polymeric according to claim 1, it is characterised in that the organic solvent be selected from toluene, hexamethylene,
Ether, tetrahydrofuran, ethanol, benzene, dimethylbenzene and dichloromethane.
8. carbon monoxide-olefin polymeric according to claim 7, it is characterised in that the organic solvent is selected from toluene and diformazan
Benzene.
9. carbon monoxide-olefin polymeric according to claim 1, it is characterised in that in the co-catalyst in aluminium and major catalyst
The mol ratio of iron is 30 to less than 900:1.
10. carbon monoxide-olefin polymeric according to claim 9, it is characterised in that aluminium and major catalyst in the co-catalyst
The mol ratio of middle iron is 100-700:1.
11. carbon monoxide-olefin polymeric according to claim 9, it is characterised in that aluminium and major catalyst in the co-catalyst
The mol ratio of middle iron is 148-196:1.
12. carbon monoxide-olefin polymeric according to claim 1, it is characterised in that described to be selected from aikyiaiurnirsoxan beta containing aluminum cocatalyst
And alkyl aluminum compound.
13. carbon monoxide-olefin polymeric according to claim 12, it is characterised in that the major catalyst containing aluminium is alkyl calorize
Compound.
14. carbon monoxide-olefin polymeric according to claim 12, it is characterised in that the formula of the alkyl aluminum compound is
AlRnXm, wherein R is each independently straight or branched C1-C8Alkyl；X is halogen；N be 1~3 integer, m be 0~2 it is whole
Number, and m+n is equal to 3.
15. carbon monoxide-olefin polymeric according to claim 14, it is characterised in that in the formula of the alkyl aluminum compound, X
For chlorine or bromine.
16. carbon monoxide-olefin polymeric according to claim 14, it is characterised in that the alkyl aluminum compound is selected from trimethyl
Aluminium, triethyl aluminum, tri-propyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium, diethylaluminum chloride and dichloride second
Base aluminium.
17. carbon monoxide-olefin polymeric according to claim 14, it is characterised in that the alkyl aluminum compound is triethyl group
Aluminium.
18. according to the carbon monoxide-olefin polymeric described in any one in claim 12-17, it is characterised in that the aikyiaiurnirsoxan beta is
C1-C4Alkylaluminoxane, wherein C1-C4Alkyl is the alkyl of straight or branched.
19. carbon monoxide-olefin polymeric according to claim 18, it is characterised in that the aikyiaiurnirsoxan beta be selected from MAO,
Modified methylaluminoxane, ethylaluminoxane and isobutyl aluminium alkoxide.
20. carbon monoxide-olefin polymeric according to claim 18, it is characterised in that the aikyiaiurnirsoxan beta is selected from MAO.
21. according to application of the carbon monoxide-olefin polymeric in ethylene oligomerization described in any one in claim 1-20.
22. application according to claim 21, it is characterised in that the temperature of the oligomerisation reaction is -20~150 DEG C.
23. application according to claim 22, it is characterised in that the temperature of the oligomerisation reaction is 0~80 DEG C.
24. application according to claim 22, it is characterised in that the temperature of the oligomerisation reaction is 5~50 DEG C.
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| CN115301290B (en) * | 2021-08-26 | 2023-09-26 | 中国石油大学(北京) | Catalyst for ethylene selective tetramerization and application thereof |
| CN116037207A (en) * | 2021-10-28 | 2023-05-02 | 中国石油化工股份有限公司 | Catalyst composition for olefin oligomerization and preparation method and application thereof |
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| CN1268106A (en) * | 1997-07-11 | 2000-09-27 | 纳幕尔杜邦公司 | Manufacture of alpha-olefins |
| CN1406217A (en) * | 2000-12-26 | 2003-03-26 | 出光石油化学株式会社 | Process for producing low polymer of ethylene |
| CN102781884A (en) * | 2010-03-26 | 2012-11-14 | 三菱化学株式会社 | Method for producing alpha-olefin oligomer |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1268106A (en) * | 1997-07-11 | 2000-09-27 | 纳幕尔杜邦公司 | Manufacture of alpha-olefins |
| CN1406217A (en) * | 2000-12-26 | 2003-03-26 | 出光石油化学株式会社 | Process for producing low polymer of ethylene |
| CN102781884A (en) * | 2010-03-26 | 2012-11-14 | 三菱化学株式会社 | Method for producing alpha-olefin oligomer |
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